The nature of the H3O+ hydronium ion in benzene and chlorinated hydrocarbon solvents. Conditions of existence and reinterpretation of infrared data

Salts of the C(3v) symmetric hydronium ion, H(3)O(+), have been obtained in the weakly basic solvents benzene, dichloromethane, and 1,2-dichloroethane. This is made possible by using carborane counterions of the type CHB(11)R(5)X(6)(-) (R = H, Me, Cl; X = Cl, Br, I) because they combine the three required properties of a suitable counterion: very low basicity, low polarizability, and high chemical stability. The existence of the H(3)O(+) ion requires the formation of three more-or-less equivalent, medium-to-strong H-bonds with solvent or anion bases. With the least basic anions such as CHB(11)Cl(11)(-), IR spectroscopy indicates that C(3v) symmetric trisolvates of formulation [H(3)O(+) .3Solv] are formed with chlorocarbon solvents and benzene, the latter with the formation of pi bonds. When the solvents and anions have comparable basicity, contact ion pairs of the type [H(3)O(+).nSolv.Carborane] are formed and close to C(3v) symmetry is retained. The conditions for the existence of the H(3)O(+) ion are much more exacting than previously appreciated. Outside of the range of solvent basicity bounded at the lower end by dichloromethane and the upper end by tributyl phosphate, and with anions that do not meet the stringent requirements of weak basicity, low polarizability of high chemical stability, lower symmetry species are formed. One H-bond from H(3)O(+) to the surrounding bases becomes stronger than the other two. The distortion from C(3v) symmetry is minor for bases weaker than dichloromethane. For bases stronger than tributyl phosphate, H(2)O-H(+)-B type species are formed that are more closely related to the H(5)O(2)(+) ion than to H(3)O(+). IR data allow criteria to be defined for the existence of the symmetric H(3)O(+) ion. This includes a linear dependence between the frequencies of nu(max)(OH) and delta(OH(3)) within the ranges 3010-2536 cm(-1) for nu(max)(OH) and 1597-1710 cm(-1) for delta(OH(3)). This provides a simple way to assess the correctness of the formulation of the proton state in monohydrated acids. In particular, the 30-year-old citation classic of the IR spectrum believed to arise from H(3)O(+) SbCl(6)(-) is re-interpreted in terms of (H(2)O)(x)().HSbCl(6) hydrates. The correctness of the hydronium ion formulation in crystalline H(3)O(+)A(-) salts (A(-) = Cl(-), NO(3)(-)) is confirmed, although, when A(-) is a fluoroanion, distortions from C(3)(v)() symmetry are suggested.     

Fries rearrangement of aryl formates: a mechanistic study by means of 1H, 2H, and 11B NMR spectroscopy and DFT calculations

1H, 2H, and 11B NMR spectroscopy has been used to study the mechanism of the Fries rearrangement of aryl formates promoted by boron trichloride by monitoring both the substrate and the Lewis acid. DFT calculations were employed to investigate the energetics of several reaction paths and to calculate NMR chemical shifts of key intermediates and products. After the formation of a 1:1 substrate-Lewis acid adduct, the rearrangement proceeds in two steps, beginning with the cleavage of the ester bond and the release of formyl chloride in situ, which, in turn, acts as a formylating agent, introducing an aldehydic functionality into the aromatic ring. The high regioselectivity (only the ortho product is obtained) is also accounted for by the proposed intermolecular, Lewis acid-assisted mechanism.     

Effects of emulsifier charge and concentration on pancreatic lipolysis. 1. In the absence of bile salts

An in vitro study is performed with sunflower oil-in-water emulsions to clarify the effects of type of used emulsifier, its concentration, and reaction time on the degree of oil lipolysis, α. Anionic, nonionic, and cationic surfactants are studied as emulsifiers. For all systems, three regions are observed when surfactant concentration is scaled with the critical micelle concentration, C(S)/cmc: (1) At C(S) < cmc, α ≈ 0.5 after 30 min and increases up to 0.9 after 4 h. (2) At C(S) ≈ 3 × cmc, α ≈ 0.15 after 30 min and increases steeply up to 0.9 after 2 h for the cationic and nonionic surfactants, whereas it remains around 0.2 for the anionic surfactants. (3) At C(S) above certain threshold value, α = 0 for all studied surfactants, for reaction time up to 8 h. Additional experiments show that the lipase hydrolyzes molecularly soluble substrate (tributirin) at C(S) > cmc, which is a proof that these surfactants do not denature or block the enzyme active center. Thus, we conclude that the mechanism of enzyme inhibition by these surfactants is the formation of a dense adsorption layer on an oil drop surface, which displaces the lipase from direct contact with the triglycerides.     

Role of surfactants on the approaching velocity of two small emulsion drops

Here we present the exact solution of two approaching spherical droplets problem, at small Reynolds and Peclet numbers, taking into account surface shear and dilatational viscosities, Gibbs elasticity, surface and bulk diffusivities due to the presence of surfactant in both disperse and continuous phases. For large interparticle distances, the drag force coefficient, f, increases only about 50% from fully mobile to tangentially immobile interfaces, while at small distances, f can differ several orders of magnitude. There is significant influence of the degree of surface coverage, θ, on hydrodynamic resistance β for insoluble surfactant monolayers. When the surfactant is soluble only in the continuous phase the bulk diffusion suppresses the Marangoni effect only for very low values of θ, while in reverse situation, the bulk diffusion from the drop phase is more efficient and the hydrodynamic resistance is lower. Surfactants with low value of the critical micelle concentration (CMC) make the interfaces tangentially immobile, while large CMC surfactants cannot suppress interfacial mobility, which lowers the hydrodynamic resistance between drops. For micron-sized droplets the interfacial viscosities practically block the surface mobility and they approach each other as solid spheres with high values of the drag coefficient.     

Interfacial layers from the protein HFBII hydrophobin: dynamic surface tension, dilatational elasticity and relaxation times

The pendant-drop method (with drop-shape analysis) and Langmuir trough are applied to investigate the characteristic relaxation times and elasticity of interfacial layers from the protein HFBII hydrophobin. Such layers undergo a transition from fluid to elastic solid films. The transition is detected as an increase in the error of the fit of the pendant-drop profile by means of the Laplace equation of capillarity. The relaxation of surface tension after interfacial expansion follows an exponential-decay law, which indicates adsorption kinetics under barrier control. The experimental data for the relaxation time suggest that the adsorption rate is determined by the balance of two opposing factors: (i) the barrier to detachment of protein molecules from bulk aggregates and (ii) the attraction of the detached molecules by the adsorption layer due to the hydrophobic surface force. The hydrophobic attraction can explain why a greater surface coverage leads to a faster adsorption. The relaxation of surface tension after interfacial compression follows a different, square-root law. Such behavior can be attributed to surface diffusion of adsorbed protein molecules that are condensing at the periphery of interfacial protein aggregates. The surface dilatational elasticity, E, is determined in experiments on quick expansion or compression of the interfacial protein layers. At lower surface pressures (<11 mN/m) the experiments on expansion, compression and oscillations give close values of E that are increasing with the rise of surface pressure. At higher surface pressures, E exhibits the opposite tendency and the data are scattered. The latter behavior can be explained with a two-dimensional condensation of adsorbed protein molecules at the higher surface pressures. The results could be important for the understanding and control of dynamic processes in foams and emulsions stabilized by hydrophobins, as well as for the modification of solid surfaces by adsorption of such proteins.     

Excitation of isomeric 1h 11/2 states in nuclear reactions induced by γ rays and neutrons and in beta decay

Isomeric ratios were measured for N=81 isotones (¹³⁵Xe, ¹³⁷Ba, ¹³⁹Ce, ¹⁴¹Nd, ¹⁴³Sm). In the experiment reported here, μ _ν ≤3±10^? J ^π=11/2^? isomers were excited in (n, γ) and (γ, n) reactions and in the β ⁺ decay of ¹³⁹Pr and ¹⁴¹Pm. In order to determine the reaction yields, use was made of the activation method involving measurement of the gamma-ray spectra of reaction products. It is found that, in the same reactions, isomeric ratios are different for isotones characterized by different atomic numbers Z. Isomeric ratios were calculated with the spectra of low-lying levels and radiative-transition probabilities established on the basis of the quasiparticle-phonon model. Good agreement between the experimental and calculated values of isomeric ratios is obtained for all isotopes invesigated here. The dependence of isomeric ratios on the atomic number Z of a nucleus is explained by the difference of reaction energies, which leads to different probabilities of excitation of activation levels through which the isomers being considered are populated.     

Ir study of the structure of palladium(ii) acetate in chloroform, acetic acid, and their mixtures in solution and in liquid-solid subsurface layers

It is found that cyclic trimer I and linear dimer II are the molecular states of palladium(II) acetate in its 1. 10^-3-0.7 M chloroform solutions. The mole fraction of dimer II is higher in dilute solutions. Even with small acetic acid (HOAc) additions the I↔II equilibrium is shifted toward I because of the variation of the composition of the outer-spheric solvation shells. The content of II in the 0.1 M solution of PdAc₂ in 50 vol. % HOAc+CHCl₃ is 10%. However, in the thin subsurface layers of this solution at the interface CaF₂ -solution, the I↔ equilibrium is slowly shifted toward II whose concentration after 60 min is 22%. This may be caused by structuring of the liquid phase in the subsurface layers during the measured time. Translated fromZhurnal Strukturnoi Khimii, Vol. 41, No. 3, pp. 540-546, May–June, 2000.     

Dipole excitations in 122Te, 126Te and 130Te

Excited states of the nuclei ¹²²Te, ¹²⁶Te and ¹³⁰Te were populated via the (γ, γ') reaction at endpoint energies of the bremsstrahlung between 4.5 and 5.5 MeV. Gamma rays were detected with a EUROBALL-CLUSTER detector and a single detector. In all nuclei several dipole transitions were identified at energies around 3 MeV. The lowest corresponding J = 1 states are interpreted as two-phonon excitations. Quasiparticle-phonon-model calculations predict one 1^? state arising from the coupling of the first quadrupole and the first octupole phonon and one 1⁺ state arising from the coupling of the first and the isovector second quadrupole phonon at about 3 MeV. The calculated transition strengths are compatible with experimental ones.     

Fundamental properties of isoelectric buffers for capillary zone electrophoresis

Different isoelectric buffers are analysed theoretically, taking into account a fundamental parameter, i.e., the ratio between intrinsic buffering power and conductivity (R=β/λ). For a model ampholyte, the above parameter is analysed both as a function of the pI and the pK_b–pK_a values. For natural pH gradients, the variation of R, connected with approaching the isoelectric point, is evaluated. A case of oligo-protic ampholytes is also considered.